Production of aliphatic hydrocarbon sulfonates



Patented Dec. 24, 1946 PRODUCTION OF ALIPHATIC HYDRO- CARBON SULFONATES Robert C. Taylor, Melrose Park, Pa., assignor to The Atlantic Refining Company, Philadelphia, Pa., a corporation of Pennsylvania No Drawing. Application March 13, 1945, Serial No. 582,571

8 Claims. 1 The present invention relates to the production of sulfuric derivatives of aliphatic hydrocarbons, and more particularly to the sulfonation or sulfation of saturated aliphatic hydrocarbons containing at least 8 carbon atoms per molecule.

It has been found that when saturated aliphatic hydrocarbons were treated with sulfonating agents such as sulfuric acid or chlorsulfonic acid at ordinary temperatures, little or no sulfonation or sulfation of the hydrocarbons was obtained. At elevated temperatures, i. e., 125 F. to 250 F. a small amount of sulfonation or sulfation occurred but the main reaction was oxidation with the production of carbonaceous or tarry materials, any sulfonic or sulfuric compounds produced being dark colored, malodorous, and commercially worthless.

I have found that the above mentioned difficulties may be overcome by carrying out the sulfonation or sulfation of aliphatic hydrocarbons in the presence of an organic carbonyl compound containing from 1 to 20 carbon atoms per molecule, and preferably from 2 to carbon atoms. The aliphatic hydrocarbons which may be treated in accordance with my invention include parafiin hydrocarbons of from 8 to 20 car bon atoms, parafiinic mineral oils and distillates, hydrocarbon waxes, oils produced in the pressing and sweating of hydrocarbon waxes, parafiinic oil fractions resulting from the selective solvent extraction of mineral oils, oils produced by the alkylation of iso-paraflins with olefins, oils chtamed by the destructive or non-destructive hydrogenation of mineral oils, oils resulting from the refining of viscous hydrocarbon oils with sulfuric acid, aluminum chloride, or other acidic agents, and the halogenated derivatives of any one or more of the above stocks. In general, any essentially saturated aliphatic hydrocarbon or hydrocarbon mixture containing from 8 to 20 carbon atoms may be utilized.

The organic carbonyl compounds which may be employed in conjunction with the hydrocarbon to be sulfonated or sulfated include aliphatic aldehydes, aliphatic carboxy acids, aliphatic esters of monoor polyhydric alcohols and carboxylic acids, and aliphatic ketones. The corresponding aromatic compounds may also be used, although less efiicaciously than the aliphatic carbonyl compounds. The aliphatic aldehydes may be exemplified by formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, valeraldehyde, and the higher homologues ofthis series, as well as the aldehydes 0f the polyhydric alcohols and unsaturated alcohols, e. g., acrolein, crotonaldehyde, and the like. The aliphatic esters, of which the lower molecular weight ones are preferred, include esters of carboxylic acids of from 1 to 20 carbon atoms, and preferably the esters of alcohols of l to 8 carbon atoms and carboxylic acids of 1 to 8 carbon atoms such as methyl, ethyl, propyl, butyl, and amyl formates, acetates, propionates, butyrate, and valerates, as well as the corresponding esters of the glycols, polygycols, and glycerol. The carboxylic acids which may be utilized, per se, are represented by formic acid, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, heptylic acid, caprylic acid, nonylic acid, capric acid, palmitic acid, margaric acid, stearic acid, and the like. The ketones are exemplified by acetone, methyl ethyl ketone, diethyl ketone, methyl propyl ketone, ethyl propyl ketone, the butyl, amyl, hexyl, heptyl, and octyl ketones, and the higher homologues containing up to 20 carbon atoms per molecule.

The quantity of organic carbonyl compound to be employed may vary from a few percent up to by volume of the hydrocarbon to be treated. Where small quantities are used, it is not worthwhile to attempt recovery following the sulfonation or sulfation, but where large volumes are used, i. e. 50% to 100% by volume, the carbonyl compound may be recovered, at least in part, by evaporation, extraction, or distillation from the sulfonated or sulfated product.

The sulfonation or sulfation may be carried out at ordinary or elevated temperatures, and preferably, is effected at temperatures between F. and F. at atmospheric or higher pressures. Strong sulfonating agents which may be employed include concentrated or fuming sulfuric acid, sulfur trioxide, or chlorsulfonic acid, the last mentioned agent being preferred. Quantities of sulfonating agent of the order of 15% to 50% by volume, based upon the hydrocarbon charge stock, have been found satisfactory.

The method of carrying out the reaction wit respect to the order of addition of the reagents also lends itself to several variations. The sulfonating agent can be dissolved or dispersed in the carbonyl compound and added to the hydrocarbon stock; the hydrocarbon stock can be added to a solution or dispersion of sulfonating agent in the carbonyl compound; or the sulfonating agent can be added to a mixture or solution of hydrocarbon stock and carbonyl compound.

Upon completion of the sulfonation 0r sulfation reaction, the desired water-soluble sulfuric derivatives may be recovered from the reaction mixture by conventional methods. For example, the

volume of ethyl acetate.

reaction mixture may be neutralized with aqueous alkali and any unsulfonated or unsuliated hydrocarbon may be separated by decantation- The aqueous solution of neutralized crude product is then evaporated to remove water and carbonyl compound if the latter is relatively low boiling, and the resulting dry, crude product is extracted with a solvent such as ethyl alcohol to dissolve the hydrocarbon sulfonate or sulfate and to leave undissolved any inorganic salts such as alkali sulfate or sulfite. The purified product may be recovered from the alcohol solution by evaporation of the alcohol.

The present invention may be further illustrated by the following examples, which, however, are not to be construed as limiting the scope thereof.

1. 100 parts by volume of light foots oil obtained by sweating crude paraflin wax, and comprising essentially a mixture of paraflinic oil and low melting waxes, was admixed with 50 parts by To this mixture was added 30 parts by volume of chlorsulfonic acid, and the resulting mixture was heated to 160 F. with constant stirring for a period of one half hour. The resulting sulfonation reaction product was then poured into a mixture of ice and caustic soda solution to effect neutralization, and the neutralized mixture was permitted to settle. Unsulfonated oil was separated from the neutral aqueous solution containing the sodium sulfonates, and the aqueous solution was then evaporated to dryness and treated with ethyl alcohol to extract the water-soluble sodium sulfonates from the inorganic salts. Upon evaporation of the alcohol from the sulfonate solution, there was obtained a yield of 92 pounds perbarrelof brown, pleasant-smelling sulfonate.

The above described operation was repeated, with the exception that no ethyl acetate was employed. The resulting product was a heavy black, malodorous tar.

2. 100 parts by volume of a mixture of low melting waxes and oil from the low temperature filter pressing of a low melting paraflin wax was admixed with parts by volume of ethyl acetate. To this mixture was added 40 parts by volume of chlorsulfonic acid, and the resulting mixture was heated to 140 F.-150 F. with constant stirring for a period of one hour. The resulting sulfonation reaction mixture was then neutralized and purified as described in Example 1, and there was obtained a yield of 83 pounds per barrel of a dark brown, pleasant-smelling sulfonate.

3. 100 parts by volume of a paraffim'c furnace oil distillate was admixed with 10 parts by volume of ethyl acetate, and to this mixture was added 40 parts by volume of chlorsulfonic acid. The resulting mixture was then heated to 140 R 150 F. with constant stirring for a period of one hour. The sulfonation reaction mixture was then neutralized and purified as described in Example 1, and there was obtained a yield of 67 pounds per barrel of a dark brown, pleasantsmelling sulfonate.

4. 100 parts by volume of 58 F. melting point paraffin slack wax was heated to 380 F.-400F. and chlorine was passed through the molten wax until approximately 1 atom of chlorine per mole of wax had been introduced and chemically combined with the wax. The chlorinated wax was then admixed with 100 parts by volume of ethyl acetate, and to the mixture was added 40 parts by volume of chlorsulfonic acid. The mixture was then heated to 140 F. with constant stirring for a period of one hour. The sulfonation reaction product was then poured into a mixture of ice and caustic soda solution to effect neutralization, and any unsulfonated chlorinated wax was removed by dccantation. The aqueous solution of crude sodium sulfonatcs was then evaporated to dryness and extracted with ethyl alcohol to dissolve the water-soluble sodium sulfonate from the inorganic salts. Upon evaporation of the alcohol from the sulfonate solution, there was obtained a yield of 91 pounds per barrel of light brown pleasant-smelling sulfonate.

The above procedure was repeated with the exception that only 10 parts by volume of ethylene acetate was employed, and there was obtained a yield of 58 pounds per barrel of a dark brown, pleasant-smelling sulfonate.

5. parts by volume of highly refined paraffinic kerosine was heated to 250 F., and chlorine was passed through the kerosine until approximately 1 atom of chlorine per mole of kerosine was introduced and chemically combined with the kerosine. The chlorinated kerosine was then cooled and admixed with 10 parts by volume of ethyl acetate, and to the mixture was added 40 parts by volume of chlorsulfonic acid. The mixture was then heated to F. with constant stirring during a period of one hour. The sulfonation reaction mixture was then neutralized and purified as described in Example 4, and there was obtained a yield of 25 pounds per barrel of a brown, pleasant-smelling sulfonate.

The above operation was repeated, with the exception that no ethyl acetate was employed. The resulting product was black, malodorous and of no commercial value.

The sulfuric derivatives, i. e., sulfonates or sulfates produced in accordance with this invention may be used as surface tension reducing agents, wetting agents, or detergents. Such products may also be admixed with other materials such as fatty acid soaps, organic or inorganic salts, mildly alkaline compounds or the like for the production of cleansing agents, scouring agents, or detergents. The sulfuric derivatives may also find application as fat-splitting agents, or as intermediates in the production of other chemical compounds including nitrosulfonates, amino sulfonates, and the like.

Herein, and in the appended claims, the term sulfuric derivatives is to be understood to comprehend sulfonic acids, salts of sulfonic acids, organic sulfates, and salts thereof. While the primary reaction involved in the process appears to be sulfonation, some sulfation may occur particularly in the treatment of the halogenated stocks. The products of the reaction may be hydrocarbon sulfonic acids or hydrocarbon substituted sulfuric acids or sulfates, or mixtures thereof, and such materials when neutralized with basic substances, for example, alkali metal or alkaline earth metal oxides, hydroxides, or carbonates, may be obtained as the corresponding salts.

I claim:

1. The method of producing a sulfuric derivative of a saturated aliphatic hydrocarbon having at least 8 carbon atoms per molecule, which comprises chlorinating said saturated aliphatic hydrocarbon and reacting said chlorinated hydrocarbon with a strong sulfonating agent in the presence of an alkyl ester of an aliphatic carboxylic acid containing from. 1 to 8 carbon atoms 5 where the alkyl group of said ester contains from 1 to 8 carbon atoms.

2. The method of producing a sulfuric derivative of a saturated aliphatic hydrocarbon having at least 8 carbon atoms per molecule, which comprises chlorinating said saturated aliphatic hydrocarbon to introduce 1 chlorine atom into said hydrocarbon and reacting said chlorinated hydrocarbon with a sulfonating agent in the presence of an alkyl ester of an aliphatic carboxylic acid containing from 1 to 8 carbon atoms where the alkyl group of said ester contains from 1 to 8 carbon atoms.

3. The method of producing a sulfuric derivative of a saturated aliphatic hydrocarbon having at least 8 carbon atoms permolecule, which comprises chlorinating said saturated aliphatic hydrocarbon and reacting said chlorinated hydrocarbon with chlorsulfonic acid in the presence of an alkyl ester of an aliphatic carboxylic acid containing from 1 to 8 carbon atoms where the alkyl group of said ester contains from 1 to 8 carbon atoms.

4. The method of producing a sulfuric derivative of a saturated aliphatic hydrocarbon having at least 8 carbon atoms per molecule, which comprises chlorinating said saturated aliphatic hydrocarbon and reacting said chlorinated hydrocarbon with a strong sulfonating agent in the presence of an ester from the group consisting of methyl, ethyl, and propyl esters of formic and acetic acids.

5. The method of producing a sulfuric derivative of a saturated aliphatic hydrocarbon having at least 8 carbon atoms per molecule, which comprises chlorinating said saturated aliphatic hydrocarbon to introduce 1 chlorine atom into said hydrocarbon and reacting said chlorinated hydrocarbon with a strong sulfonating agent in the presence of an ester from the group consisting of methyl, ethyl, and propyl esters of formic and acetic acids.

6. The method of producing a sulfuric derivative of a saturated aliphatic hydrocarbon having at least 8 carbon atoms per molecule, which comprises chlorinating said saturated aliphatic hydrocarbon to introduce 1 chlorine atom into said hydrocarbon and reacting said chlorinated hydrocarbon with chlorsulfomc acid in the presence of an ester from the group consisting of methyl, ethyl, and propyl esters of formic and acetic acids.

7. The method of producing a sulfuric derivative of a saturated aliphatic hydrocarbon having at least 8 carbon atoms per molecule, which comprises chlorinating a low melting paraflin wax and reacting said chlorinated wax with a strong sulfonating agent in the presence of an alkyl ester of an aliphatic carboxylic acid containing from 1 to 8 carbon atoms where the alkyl group of said ester contain from 1 to 8 carbon atoms.

8. The method of producing a sulfuric derivative of a saturated aliphatic hydrocarbon having at least 8 carbon atoms per molecule, which comprises chlorinating a parafflnic kerosine and reacting said chlorinated paraflinic kerosine with a strong sulfonating agent in the presence of an alkyl ester of an aliphatic carboxylic acid containing from 1 to 8 carbon atoms where the alkyl group of said ester contains from 1 to 8 carbon atoms.

ROBERT C. TAYLOR. 

